In this paper, the photochemistry of glyoxal−hydroxylamine (Gly−HA) complexes is studied using FTIR matrix isolation spectroscopy and ab initio calculations. The irradiation of the Gly−HA complexes with the filtered output of a mercury lamp (λ > 370 nm) leads to their photoconversion to hydroxyketene−hydroxylamine complexes and the formation of hydroxy(hydroxyamino)acetaldehyde with a hemiaminal structure. The first product is the result of a double hydrogen exchange reaction between the aldehyde group of Gly and the amino or hydroxyl group of HA. The second product is formed as a result of the addition of the nitrogen atom of HA to the carbon atom of one aldehyde group of Gly, followed by the migration of the hydrogen atom from the amino group of hydroxylamine to the oxygen atom of the carbonyl group of glyoxal. The identification of the products is confirmed by deuterium substitution and by MP2 calculations of the structures and vibrational spectra of the identified species.
Keywords: carbonyl; hemiaminal; hydroxyketene; infrared spectroscopy; matrix isolation; photochemistry.